Exchange-Correlation Potentials and Energy Densities through Orbital Averaging and Aufbau Integration

Abstract

Exchange-correlation potentials vxc and energy densities exc are derived for integer and fractional electron counts using an orbital-averaged Kohn-Sham inversion procedure. The reference densities for inversion come from full configuration interaction in a Slater orbital basis. The orbital-averaged potentials accurately capture key features of vxc, including the asymptotic negative one over r decay and the step discontinuity associated with integer electron transitions for the series of atoms He through Ne. Exchange-correlation energy densities exc are produced through an aufbau path integral. The energy densities reach good agreement with total Exc values. By providing full configuration interaction-derived Kohn-Sham quantities, including vxc, exc, and step contributions, this workflow can be instrumental in the development of improved XC functionals that bridge wavefunction-level accuracy with the computational efficiency of density functional theory.

References in corpus (23)

• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Localization and delocalization errors in density functional theory and implications for band-gap prediction
• Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
• Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory
• Fractional spins and static correlation error in density functional theory
• Fast Semistochastic Heat-Bath Configuration Interaction
• Delocalization errors in density functional theory are essentially quadratic in fractional occupation number
• Excited States of Methylene, Polyenes, and Ozone from Heat-Bath Configuration Interaction
• Numerical Methods for the Inverse Problem of Density Functional Theory
• Discontinuities of the exchange-correlation kernel and charge-transfer excitations in time-dependent density functional theory
• Reduction of Electronic Wavefunctions to Kohn-Sham Effective Potentials
• Inverse Kohn-Sham Density Functional Theory: Progress and Challenges
• One-electron self-interaction and the asymptotics of the Kohn-Sham potential: an impaired relation
• Kohn-Sham potentials in exact density-functional theory at non-integer electron numbers
• How is the derivative discontinuity related to steps in the exact Kohn-Sham potential?
• Improved method for generating exchange-correlation potentials from electronic wave functions
• Nonanalyticity of the optimized effective potential with finite basis sets
• Exchange and correlation near the nucleus in density functional theory
• Exchange Correlation Potentials from Full Configuration Interaction in a Slater Orbital Basis
• Density-potential inversion from Moreau-Yosida regularization
• Exact and model exchange-correlation potentials for open-shell systems
• Examining the Impact of Local Condition Violations on Energy Computations in DFT